Colloidal Particles with Triangular Patches.

Self-assembling colloidal particles into clathrate hydrates requires the particles to have tetrahedral bonds in the eclipsed conformation. It has been suggested that colloidal particles with eclipsed triangular-shaped patches can form clusters in the eclipsed conformation that leads to colloidal clathrate hydrates. However, in experiments, patches have been limited to circular shapes due to surface energy minimization. Here, we extend the particle synthesis strategy and show that colloidal particles with triangular patches can be readily fabricated by controlling the viscosity of the liquid oil droplets during a colloidal fusion process. The position, orientation, curvature, shape, and size of the patches are all exclusively determined by the intrinsic symmetry of the colloidal clusters, resulting in dipatch particles with eclipsed patches and tetrahedral patchy particles with patch vertices pointing toward each other. Patch curvature can be controlled by tuning the viscosity of the oil droplets and using different surfactants. Using strain-promoted azide-alkyne cycloaddition, single-stranded DNA can be selectively functionalized on the patches. However, after annealing these particles, dipatch particles form chains because the patches are too small to form clathrate hydrates. Under certain conditions, tetrahedral triangular patchy particles should prefer the eclipsed conformation, as it maximizes DNA hybridization. However, we observe random aggregates, which result from having triangular patches that are too big. We estimate that tetrahedral patchy particles that can crystallize need to be less than 1 µm in diameter.

Colloidal diamond.

Self-assembling colloidal particles in the cubic diamond crystal structure could potentially be used to make materials with a photonic bandgap1-3. Such materials are beneficial because they suppress spontaneous emission of light1 and are valued for their applications as optical waveguides, filters and laser resonators4, for improving light-harvesting technologies5-7 and for other applications4,8. Cubic diamond is preferred for these applications over more easily self-assembled structures, such as face-centred-cubic structures9,10, because diamond has a much wider bandgap and is less sensitive to imperfections11,12. In addition, the bandgap in diamond crystals appears at a refractive index contrast of about 2, which means that a photonic bandgap could be achieved using known materials at optical frequencies; this does not seem to be possible for face-centred-cubic crystals3,13. However, self-assembly of colloidal diamond is challenging. Because particles in a diamond lattice are tetrahedrally coordinated, one approach has been to self-assemble spherical particles with tetrahedral sticky patches14-16. But this approach lacks a mechanism to ensure that the patchy spheres select the staggered orientation of tetrahedral bonds on nearest-neighbour particles, which is required for cubic diamond15,17. Here we show that by using partially compressed tetrahedral clusters with retracted sticky patches, colloidal cubic diamond can be self-assembled using patch-patch adhesion in combination with a steric interlock mechanism that selects the required staggered bond orientation. Photonic bandstructure calculations reveal that the resulting lattices (direct and inverse) have promising optical properties, including a wide and complete photonic bandgap. The colloidal particles in the self-assembled cubic diamond structure are highly constrained and mechanically stable, which makes it possible to dry the suspension and retain the diamond structure. This makes these structures suitable templates for forming high-dielectric-contrast photonic crystals with cubic diamond symmetry.